Oxime carbamate phosphate,phosphonate,phosphinate and phosphoroamidates

ABSTRACT

WHEREIN R7 IS SELECTED FROM THE GROUP CONSISTING OF ALKYL HAVING FROM 1 TO 8 CARBONS INCLUSIVE, TRICHLOROMETHYL AND LOWER ALKENYL HAVING FROM 2 TO 4 CARBON ATOMS, INCLUSIVE, AND THE RADICAL -(CH2)M-SR IN WHICH M IS 1 OR 2, R IS ALKYL HAVING 1 TO 6 CARBON ATOMS, ALKENYL HAVING 2 TO 4 CARBON ATOMS, PHENYL, SUBSTITUTED PHENYL IN WHICH SAID SUBSTITUENTS ARE SELECTED FROM THE GROUP HALOGEN, LOWER ALKYL HAVING 1 TO 4 CARBON ATOMS, INCLUSIVE, AND LOWER ALKOXY HAVING 1 TO 4 CARBON ATOMS, INCLUSIVE, LOWER ALKYL SULFONATO HAVING FROM 1 TO 6 CARBON ATOMS, INCLUSIVE, LOWER ALKYL SUBSTITUTED THIOPHOSPHORYL WHEREIN THE LOWER ALKYL GROUPS INDEPENDENTLY CONTAIN FROM 1 TO 4 CARBON ATOMS, INCLUSIVE, AND 2,2,2-TRICHLORO-1-HYDROXYETHYL-4CYANOPHENYL, 2,4,5 - TRICHLOROPHENYL AND 4 - METHYLTHIOPHENYL.   -CO-R7   ISAN N-CONTAINING HETEROCYCLIC MEMBER SELECTED FROM THE GROUP CONSISTING OF MORPHOLINO, PIPERAZINO, PYRROLIDINO, PIPERADINO, HEXAMETHYLENAMINO, PYRRYL, INDOLYL, IMIDAZOLYL, BENZIMIDAZOLYL, PYRAZOLYL, 1,3-OXAZOLIDINO, AND 1,3-THIAZOLIDINO, ESTERS OF THE TYPE   -N(-R5)-R6   IN WHICH R5 AND R6 ARE INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, ALKYL HAVING FROM 1 TO 10 CARBON, INCLUSIVE, SUBSTITUTED ALKYL HAVING 1 TO 6 CARBON ATOMS INCLUSIVE, SAID SUBSTITUTES SELECTED FROM THE GROUP CONSISTING OF HYDROXY, HALOGEN, AMINO, DI-LOWER-ALKYL AMINO, LOWER ALKOXY, AND TETRAHYDROFURYL, LOWER ALKENYL HAVING FROM 2 TO 4 CARBON, INCLUSIVE, CARBALKOXY ALKYL HAVING A TOTAL OF FROM 3 TO 8 CARBON ATOMS, INCLUSIVE CYCLOALKYL HAVING FROM 3 TO 6 CARBON ATOMS, INCLUSIVE, PIPERAZINO, 2-THIAZOLYL, PHENYL, NAPHTHYL, SUBSTITUTED PHENYL WHEREIN SAID SUBSTITUENTS ARE SELECTED FROM THE GROUP CONSISTING OF HALOGEN, LOWER ALKYL, LOWER ALKOXY, LOWER THIOALKYL, LOWER DIALKYLAMINO IN WHICH SAID LOWER ALKYL AND LOWER ALKOXY MOIETIES HAVE FROM 1 TO 4 CARBON ATOMS, INCLUSIVE, NITRO, CYANO, TRIFLUOROMETHYL, AND COMBINATIONS THEREOF, AND IN WHICH   -CO-N(-R5)-R6   IN WHICH Z IS OXYGEN OR SULFUR, R4 IS LOWER ALKYL HAVING FROM 1 TO 4 CARBON ATOMS, INCLUSIVE, AND B-CHLORO-LOWERALKYL HAVING FROM 2 TO 4 CARBON ATOMS, CARBAMATES OF THE TYPE   -CO-Z-R4   IN WHICH X AND Y ARE INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF OXYGEN AND SULFUR, R IS SELECTED ROM THE GROUP LOWER ALKYL OR LOWER ALKOXY, HAVING FROM 1 TO 6 CARBON ATOMS INCLUSIVEM R1 IS SELECTED FROM THE ROUP CONSISTING OF LOWER ALKYL OR LOWER ALKOXY HAVING FROM 1 TO 6 CARBON ATOMS, INCLUSIVE, AMINO, LOWER ALKYL-SUBSTITUTED AMINO AND PHENYL, Q IS SELECTED FROM THE GROUP CONSISTING OF DIVALENT TETRAMETHYLENEDIENE-1,3, LOWER ALKYL-SUBSTITUTED ALKYL HAVING FROM 1 TO 4 CARBON ATOMS INCLUSIVE, EACH, NITRO, HALOGEN AND COMBINATIONS THEREOF, AND LOWER DIALKYL SUBSTITUTED THIONOPHOSPHORLOXY, R2 IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, LOWER ALKYL HAVING FROM 1 TO 4 CARBON ATOMS, AND PHENYL, AND R3 IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, SUBSTITUTED CARBONATE AND THIOCARBONATES OF THE TYPE OXIME CARBAMATE PHOSPHATES, PHOSPHONATES, PHOSPHINATES AND PHOSPHOROAMIDATES HAVING THE GENERAL FORMULA:   R-P(=X)(-R1)-Y-(Q-PHENYLENE)-C(-R2)=NO-R3

United States Patent Oflice 3,733,375 Patented May 15., 1973 us or.260-938 44 Claims ABSTRACT OF THE DISCLOSURE Oxime carbamate phosphates,phosphonates, phosphinates and phosphoroamidates having the generalformula:

in which X and Y are independently selected from the group consisting ofoxygen and sulfur; R is selected from the group lower alkyl or loweral-koxy, having from 1 to 6 carbon atoms inclusive; R is selected fromthe group consisting of lower alkyl or lower alkoxy having from 1 to 6carbon atoms, inclusive, amino, lower alkyl-substituted amino andphenyl; Q is selected from the group consisting of divalenttetramethylenediene-l,3, lower alkoxy or lower alkyl having from 1 to 4carbon atoms inclusive, each, nitro, halogen and combinations thereof,and lower dialkyl substituted thionophosphoryloxy; R is selected fromthe group consisting of hydrogen, lower alkyl having from 1 to 4 carbonatoms, and phenyhand R is selected from the group consisting ofhydrogen; substituted carbonate and thiocarbonates of the type in whichZ is oxygen or sulfur, R is lower alkyl having from 1 to 4 carbon atoms,inclusive, and ,B-chloro-loweralkyl having from 2 to 4 carbon atoms;carbamates of the yp group consisting of halogen, lower alkyl, loweralkoxy,

lower thioalkyl, lower dialkylamino in which said lower alkyl and loweralkoxy moieties have from 1 to 4 carbon atoms, inclusive, nitro, cyano,trifluoromethyl, and combinations thereof; and in which is anN-containing heterocyclic member selected from the group consisting ofmorpholino, piperazino, pyrrolidino, piperadino, hexamethylenamino,pyrryl, indolyl, irnidazolyl, benzimidazolyl, pyrazolyl,1,3-oxazolidino, and 1,3-thiazolidino; esters of the type wherein R isselected from the group consisting of alkyl having from 1 to 8 carbonsinclusive, trichloromethyl and lower alkenyl having from 2 to 4 carbonatoms, inclusive,

and the radical (CH SR in which m' is 1 or 2, R is alkyl having 1 to 6carbon atoms, alkenyl having 2 to 4 carbon atoms, phenyl, substitutedphenyl in which said substituents are selected from the group halogen,lower alkyl having 1 to 4 carbon atoms, inclusive, and lower alkoxyhaving 1 to 4 carbon atoms, inclusive; lower alkyl sulfonato having from1 to 6 carbon atoms, inclusive; lower alkyl substituted thiophosphorylwherein the lower alkyl groups independently contain from 1 to 4 carbonatoms, inclusive, and 2,2,2-trichloro-l-hydroxyethyl-4- cyanophenyl,2,4,5 trichlorophenyl and 4 methylthiophenyl.

The compounds are useful as insecticides, animal contact and systemicparasiticides, herbicides and foliar fungi protectants. Representativecompounds are:

3- [0,0-diethylphosphorothioyl] benzaldoxime;

3- [O- (0,0-diethylphosphorothioyl) ]benzaldoximin0-N'- methylcarbamate;

4- [O- 0,0-diethylphosphorothioyl) -acetophenone oxime;

4- 0,0-diethylphosphorothioyl] -acetophenoneoximino-N-methyl carbamate;and

4- [O,O-diethylphosphorothioyl] -acetophenoneoximino acetate;

4- O- 0,0-diethylphosphorothioyl) -benzaldoximino-N'- morpholinylcarbamate;

4- [O- (0,0-diethylphosphorothioyl) ]-benzaldoximino-N'- piperidylcarbamate;

4- [O-(0,0-diethylphosphorothioyl) ]-benzaldoximino-N'-azepinocarbamate;

O-ethyl-O- [4-(N'-methylcarbamyl-oximino) phenyl] -N- methylarnidophosphorothioate;

4- [O- 0,0-diethylphosphorothioyl) ]-benzaldoximino-N-(B-N",N"-diethy1-aminoethyl)-carbamate.

This application is a continuation of then copending application Ser.No. 730,588, filed May 20, 1968, now abandoned, which in turn is acontinuation-in-part of then copending application Ser. No. 646,467,filed June 16, 1967, now abandoned.

This invention relatesto certain novel phosphorus containing compoundswhich can be used as insecticides, animal parasiticides, both contactand systemic, herbicides and foliage fungi protectants. Morespecifically, this invention relates to certain substituted organo-oximephosp'hates, phosphonates, phosphinates and phosphoroamidates and to thepreparation and utility of the compounds as insecticides, animalsystemic parasiticides, herbicides and foliage fungicides.

The compounds comprising the instant class of compounds correspond tothe general formula:

in which X and Y are independently selected from the group consisting ofoxygen and sulfur; R is selected from the group lower alkyl or loweralkoxy, having from 1 to 6 carbon atoms inclusive; R is selected fromthe group consisting of lower alkyl or lower alkoxy having from 1 to 6carbon atoms, inclusive, amino, lower alkyl-substituted amino, andphenyl; Q is selected from the group consisting of divalenttetramethylenediene-l,3, lower alkoxy or lower alkyl having from 1 to 4carbon atoms inclusive, each, nitro, halogen and combinations thereof,and lower dialkyl substituted thionophosphoryloxy; R is selected fromthe group consisting of hydrogen, lower alkyl having from 1 to 4 carbonatoms and phenyl; and R is selected from the group consisting of hydrgensubstituted carbonate and thiocarbonates of the type in which Z isoxygen or sulfur, R is lower alkyl having from 1 to 4 carbon atoms,inclusive, and B-chloroloweralkyl having from 2 to 4 carbon atoms;carbamates of the type in which R and R are independently selected fromthe group consisting of hydrogen, alkyl having from 1 to carbons,inclusive, substituted alkyl having 1 to 6 carbon atoms inclusive, saidsubstituent is selected from the group consisting of hydroxy, halogen,amino, di-lower alkyl amino, lower alkoxy and tetrahydrofuryl; loweralkenyl having from 2 to 4 carbons, inclusive, carboalkoxy alkyl havinga total of from 3 to 8 carbon atoms, inclusive, cycloalkyl having from 3to 6 carbon atoms, inclusive, piperazino, Z-thiazolyl, phenyl, naphthyl,substituted phenyl wherein said substituents are selected from the groupconsisting of halogen, lower alkyl, lower alkoxy, lower thioalkyl, lowerdialkylamino in which said lower alkyl and lower alkoxy moieties havefrom 1 to 4 carbon atoms, inclusive, nitro, cyano, trifiuoromethyl andcombinations thereof; and in which is an N-containing heterocyclicmember selected from the group consisting of morpholino, piperazino,pyrrolidino, piperadino, hexamethylenamino, pyrryl, indolyl,irnidazolv1, benzirnidazolyl, pyrazolyl, 1,3-0xazolidino, and 1,3-thiazolidino; esters of the type it -CR1 wherein R is selected from thegroup consisting of alkyl having from 1 to 8 carbons, inclusivetrichloromethyl and lower alkenyl having from 2 to 4 carbon atoms,inclusive, and the radical -(CH SR in which in is 1 or 2, R

is alkyl having 1 to 6 carbon atoms, alkenyl having 2 to 4 carbon atoms,phenyl, substituted phenyl in which said substituents are selected fromthe group halogen, lower alkyl having 1 to 4 carbon atoms, inclusive andlower alkoxy having 1 to 4 carbon atoms, inclusive; lower alkylsulfonato having from 1 to 6 carbon atoms, inclusive; lower alkylsubstituted thiophosphoryl wherein the lower alkyl groups independentlycontain from 1 to 4 carbon atoms, inclusive; and2,2,2-trichloro-1-hydroxyethyl-4- cyanophenyl, 2,4,5-trichlorophenyl and4-methylthiophenyl. Lower alkyl and lower alkoxy includes those membersof the groups which contain the indicated number of carbon atoms in bothstraight chain and branched chain configurations. Lower alkenyl includesthose members of the group containing a double bond and containing from2 to 4 carbon atoms, inclusive. When Q is divalent tetramethylene-1'.3it is bonded to the 2,3 or 3,4 carbon atoms of the phenyl ring, therebybecoming either a or 5 naphthyl, respectively. Also included herein is amethod of preparing, using, and applying the compositions.

The compounds herein described can be prepared by several methods. Onesuch general method applicable in preparing the compounds is thecondensation between the appropriate substituted phosphorus-containingoxy or thio benzaldehyde, e.g. phosphoro, phosphono, phosphino, andhydroxylamine hydrochloride in order to prepare the correspondingbenzaldoxime. The benzaldoxime can be further reacted with appropriatesubstituted isocyanate, substituted acid chlorides, substitutedchloroformate, substituted chlorothiolformate, substituted sulfonylchloride, monosubstituted carbamyl chloride, N,N-disubstitute'd carbamylchloride, substituted phosphoryl chloride, substituted thionophosphorylchloride, or anhydrous trichloro-acetaldehyde. When R is to be loweralkyl, an appropriate substituted-phosphoryl orsubstituted-thiophosphoryl lower alkyl phenylketone is condensed withhydroxylamine hydrochloride to prepare the corresponding ketoxime.Another method useful for the preparation of carbamyl derivatives isfirst the condensation of phosgene with the aldoxime followed by thecondensation with a primary or secondary amine. The reactions proceedreadily in the liquid phase. The employment of a solvent is also useful,facilitating processing, as well as agitation of the reactants. Solventssuch as water, benzene, toluene, chloroform, aqueous ethanol and thelike, can be employed. When using derivatives containing the aldoxime,it is preferred to carry out the reaction in the presence of a hydrogenhalide acceptor such as sodium carbonate, triethylamine, pyridine,picoline and the like, which are used as catalysts. Similarly, in thecondensation reaction to prepare secondary carbamyl derivatives, thereaction is preferably conducted in the presence of a hydrogen halideacceptor.

The reactions are carried out at temperatures that permit operation inthe liquid phase. These temperatures are between about room temperatureand reflux temperature of the solvent, if one is employed. Preferably,the reaction mixture is refluxed, usually at an elevated temperature.The ketoxime can be reacted with functional moieties as described suprafor the benzaldoxime.

It now has been discovered that the new compositions disclosed hereinare distinguished as useful as insecticides, herbicides, foliar fungiprotectants and are particularly effective as systemic parasiticidalagents for animals.

The compounds of the present invention are prepared in accordance withthe following illustrative examples.

EXAMPLE 1 Prepartion of the intermediate3-[O-(0,0-diethylphosphorothioyl)] benzaldehyde In 200 ml. of methylethyl ketone in a 500 ml. 3-neck flask are combined 24.4 g. (0.2 mole)3-hydroxybenzaldehyde, 37.8 g. (0.2 mole)0,0-diethylthiophosphorylchloride. and 16.4 g. (0.12 mole) potassiumcarbonate. The

mixture is stirred and heated under reflux for 4 hours, cooled, andpoured into 300 ml. of water. The mixture is filtered free of solid andis extracted with two 150 ml. portions of chloroform. The chloroformphases are combined, dried with anhydrous MgSO, and the solventevaporated. There is obtained 54.7 g. (99.5 percent of theory) of thetitle intermediate-n :1.5239. r r 7 Preparation of3-[0,0-diethylphosphorothioyl] .benzaldoxime EXAMPLE 2 Preparation of3-[O-(0,0-diethylphosphorothioyl)] benzaldoximino-N'-methyl carbamate'Ie'n grams (0.034 mole) of3-[0-(0,0-diethylphosphorothioyl)]-benzaldoxime dissolved in 10 ml. ofacetone is treated with an excess of methylisocyanate. The mixture ispoured into 200 ml. of benzene. The benzene is washed with 2-50 ml.portions of water, dried with anhydrous MgSO and evaporated. There isobtained a yield of 11.2 g. (93.3 percent of theory) of the titlecompound, n =1.5394.

EXAMPLE 3 Preparation of 4-[0-(0,0-diethylphosphorothioyD] acetophenoneoxime In 150 ml. of 80 percent aqueous ethanol are combined 56.2'g.)0.195 mole) 4-[0(0,O -diethylphosphorothioyb]- acetophenone, 17.4 g.(0.25 mole) hydroxylamine hydrochloride, and 4 gms. (0.1 mole) sodiumhydroxide. The mixture is heated and refluxed for 5 min., cooled,acidified with concentrated hydrochloride acid and extracted with two 15ml. portions of chloroform. The chloroform phases are combined, driedwith anhydrous MgSO and evaporated. There is obtained 55.0 g. (93.5percent of theory) of the title compound, n =1.5393.

EXAMPLE 4 Preparation of 4-[O-(0,0-diethylphosphorothioy1)]-acetophenoneoximino-N-methyl carbamate By an analogous procedure asgiven in Example 2, supra, 10.0 g. (0.03 mole) of 4-[O-(0,0-diethylphosphorothioyl)] acetophenoneoxime is reacted withmethyl isocyanate. There was obtained 11.5 g. (96.9 percent of theory)of the title compound.

EXAMPLE Preparation of4-[0,0-diethylphosphorothioyl]-acetophenoneoximino acetate The followingprocedure also can be used with a carbamyl chloride, sulfonyl chlorideor chloroformate in order to obtain compounds that include therespective functional molieties typical of said reactants.

In 150 ml. of benzene 10.0 g. (0.03'mole) of 4-[4-(O, Odiethylphosphorothioyl)]-acetophenoneoxime, 3.2 g. (0.04 mole) ofacetylchloride, and 4.1 g. (0.04 mole) of triethylamine are combined.The mixture is heated and refluxed for about one hour. The cooledreaction mixture is washed with two 50 ml. portions of water. Thebenzene phase is dried with anhydrous magnesium sulfate and then thebenzene evaporated. There is obtained 11.0

. g. (96.5 percent of theory) of the title compound n EXAMPLE 6 Seven.grams (0.07 mole) of phosgene in 150 ml. of anhydrous diethyl ether isadded to a 500 ml. 3-neck flask fitted with a stirrer, dropping funnel,Dry Ice condenser, and thermometer. The solution is stirred and cooledto 10 C. with an ice bath. N,N-dimethylaniline, 8.6 g. (0.07 mole) isadded over a period of 30 minutes. 4-[O-(0,0- diethylphosph0rothioyl)]benzaldoxime, 14.5 g. (0.05 mole) in 50 ml. of anhydrous diethyl etheris added over a period of 30 min. The temperature of the reactionmixture is maintained between 10 and 15 C. After the addition iscomplete, the mixture is stirred for one hour at 15 C. A solution of17.4 grams (0.2 mole) of morpholine and 10 ml. of water is added to thestirring reaction mix ture at such a rate that the temperature does notexceed 15 C. After the addition is complete, the mixture is stirred fortwo hours at room temperature. The mixture is diluted with 200 ml. ofether and washed consecutively with ml. of water, 100 ml. 1 N HCl, andagain with 100 ml. of Water. The ether phase is dried with anhydrousMgSO and evaporated to yield 18 grams (89.8% of theory) of 4- [O-(0,0-diethylphosphorothioyl) ]-benzaldoximino-N'- morpholinylcarbamate,n =1.5423.

EXAMPLE 7 Preparation of 4-[O-(0,0-diethylphosphorothioyl)]benzaldoximino-N-(fl-hydroxyethyl) carbamate Seven grams (0.07 mole) ofphosgene, 8.6 grams (0.07 mole) of N,N-dimethylaniline and 14.5 grams(0.05 mole) of 4-[0-(0,0-diethylphosphorothionyl)] benzaldoxime arereacted in 200 ml. anhydrous diethyl ether by the procedure described inExample 6. The etherical solution is cooled to 10 C. and a solution of6.1 grams (0.1 mole) of ethanolamine and 10 ml. of water is added atsuch a rate that the temperature does not exceed 15 C. After theaddition is complete, the mixture is stirred at room temperature for onehour. The product is isolated by the procedure described in Example 6.There is obtained a 17.8 grams (94.8% of theory) of the title compound,n =1.5423.

EXAMPLE 8 Preparation of 4-[O-(0,0-diethy1phosphorothioyl)]benzaldoximino-N' [fl-(N",N-diethylamino)ethyl1carbamate Seven grams(0.07 mole) of phosgene, 8.6 grams (0.07 mole) of N,N-dimethylaniline,and 14.5 grams (0.05 mole) of 4-[O-(0,0-diethyl phosphorothioyl)benzaldoxime are reacted in 200 ml. of anhydrous diethyl ether by theprocedure described in Example 6. The etherical solution is washed with100 ml. of ice cold 1 N HCl and returned to the reaction flask where itis stirred and cooled to 10 C. A solution of 11.6 grams (0.1 mole) of,6-N,N- diethyl ethylenediamine and 10 ml. of water is added to theetherical solution at such a rate that the temperature does not exceed15 C. After the addition is complete, the mixture is stirred at roomtemperature for one hour. An additional 100 ml. of anhydrous diethylether is added, and the mixture is washed with 50 ml. of ice cold 1 NNaOH followed by two 50 m1. portions of water. The ether phase is driedwith anhydrous MgSO and evaporated. There is obtained 11.3 grams (51.8%of theory) of the title compound, n 1.53l0.

The following is a table of the compounds prepared according to theaforedescribed procedures. Compound numbers have been assigned to eachcompound and are then used for identification throughout the balance ofthe application.

TAB LE I--Oontinued Compound number mmm .3 i .3 a Z. 3:; .3 ii. a a a3:2. 3:. m an HR Han n HH 3 HHH a H HHH H .3 H H H HH HHH HcmwmficoHHHHHHHHHHHHO HHHHHHHHHHHHHCCCCHHCCHHHmmCOCHMHHHHHCHCCGHHCWHCHHHHHHH QCCHHHCOCHHHHHHHHHH H m m 1 m cHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHMHHHHHHHHHHHMannHHHHHHHMHHHHHHHHHHHHHHMHHHHHHHHHfiwnnnwwmnnnnnnunnwnOOOOOOOOOOOOOOOOOOOOOQOOOOOOOOOOOOOODOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOOSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSS See footnotes at end of table.

TABLE I-Continued Compound number R R1 X Y Q (P? R2 o 021150 s o 3-NO: 4H C(O)NH(3-CH S-phenyl) 1. 5333 0211 0 3 0 3-NO;, 4 HC(O)NH(CHzCH=CHz) 1. 5463 CHI; S O H 4 CH3 C(O)NH(C4H9) 1.5493 01115 S OH 4 C H; C (O) NH -O F -phenyl 1. 5632 02H, 5 0 H 4 H C(O)NI-I(3-C F-plienyl) 1. 5507 Dec. 9 Dark oil. 3 Semi-solid. 4 Waxy solid. 53,4-tetramethylonedieue-l, 3'. Phenyl. ositlon of phenyl substitution byR2 relative to the phosphorus containing group.

[(I3=NOR3] H ERBICIDAL SCREENING TESTS TABLE H 'Cnflnued Novelcompositions are phytotoxic compounds which 1r Compound are useful andvaluable in controlling various plant 0 number 09 Ft WG PW Mt CDspecies.

In the method of the present invention for controlling undesirableplants which comprises applying an herbi- I+ I II I I cidally effectiveamount of the above-described compounds to the area in which control isdesired, an herbi- I I II I I cide is used to mean a compound whichcontrols or modifies the growth of plants. By an herbicidally effectiveI I I amount is meant an amount of compound which causes a modifyingeffect upon the growth of plants. Such modi- I I II If I fying effectsinclude all deviations from natural develop- I ment, for example,killing, retardation, defoliation, desiccation, regulation, stunting,tillering, stimulation, dwarf- I if 1 ing and the like. By plants it ismeant germinant seeds, emerging seedlings, and established vegetationincluding the roots and above-ground portions. I III III I The compoundsof this invention were tested as herbij 1 i cides in the followingmanner.

Pre-emergence herbicide test.The seeds of crab grass (CG) (Digitariasanguinalis (L) Scop.), foxtail (Ft) 142-. III I- iii (Setaria glauca(L) Beauv.), watergrass (WG (Eclzinochloa crusgalli (L.) Beauv.),pigweed (PW) (Amaranifgs iiigfigifiglfi rating' thus retroflexws (L.),mustard (Md) (Brassica juncea 1 (L.) Coss.), and curly dock (CD) (Rumexcrispus (L.

were planted in individual rows one-half inch deep in 40 TABLE In SantaCruz sandy loam soil contained in compressed [Pvswmergentlwrbiddutestlpaper flats 8%" x 6 /2", which are 2% deep. Enough Compound seeds wereplanted to give about thirty to fifty plants of WG R0 Md PB each of theweed species in each fiat. The flats were watered after planting. Thefollowing day each flat was sprayed at the rate of 20 pounds of thecandidate com- I+ I+ pound under test in 80 gallons of solution peracre. An atomizer was used to spray the solution on the soil sur- I I Iface. The flats were placed in a green house at 80 F. and 'i wateredregularly. Two weeks later the degree of weed I 1+ I++ II+ control wasdetermined by comparing the amount of germination and growth of eachweed in the treated flats I I I with weeds in several untreated controlflats. The results i++ of this test are reported in Table II. I I++Post-emergence herbicide test-The seeds of four f weed species, crabgrass (CG) (Digitaria sanguinalis I I I+ (L.) Scop.), watergrass (WG)(Echinochloa crusgalli (L.) Beauv.), red oats (R0) (Avena 'sativa (L.)),mus- I I I++ tard (Md) (Brassica jumcea ('L.) Coss.), and one crop,

pinto beans (PB) (Phaseolus vulgar IS) were planted in individual rowsas described in the pre-emergence test, supra. Two weeks after planting,the plant foliage was I I II sprayed with a 0.5% solution of the testcompounds at a rate equivalent to 12.5 pounds/acre. The treated plants II were placed back in the greenhouse. Injury ratings were recorded 14days after treatment. The rating system is I I the same as that used inthe pre-emergence test. Table III lists the results obtained therefrom.I I II+ TABLE II. i [Pro-Emergent Herbicide Test 1 Compound number CG FtWG PW Mt CD 75 See footnotes at end of table.

TABLE III-Continued Compound number CG WG R Md PB 2+ in r 11 1+ 1 if ii+Herbieidal activity rating:

= light injury.

+=Moderate iniury- ++=Severe lnlllry or death The compounds of thepresent invention are used as preemergence or post-emergence herbicidesand are applied in a variety of ways at various concentrations. Inpractice, the compounds are formulated with an inert carrier, utilizingmethods well known to those skilled in the art, thereby making themsuitable for application as dusts, sprays, or drenches and the like inthe form and manner required. The mixtures can be dispersed in waterwith the aid of a wetting agent or they can be employed in organicliquid compositions, oil and water, water in oil emulsions, with orwithout the addition of wetting, dispersing or emulsifying agents. Theamount applied depends upon the nature of theseeds or plants to becontrolled and the rate of application varies from 1 to approximately 50pounds per acre.

The phytotoxic compositions of this invention are applied to the plantsin the conventional, manner. Thus, the dust and liquid compositions canbe applied to the plant by the use of power-dusters, boom and handsprayers and spray-dusters. The compositions canalso be applied fromairplanes as a dust or a spray because they are effective in very lowdosages. In order to modify or control growth of germinating seeds oremerging seedlings, the dust and liquid compositions are applied to thesoil according to conventional methods and are preferably distributed inthe soil to a depth of at least /2-inch below the soil surface. It isnot necessary that the phytotoxic compositions be admixed with the soilparticles and these compositions can be applied merely by spraying orsprinkling the surface of the soil. The phytotoxic compositions ofthisinvention can also be applied by addition to irrigation water suppliedto the field to be treated. This method of application permits thepenetration of the compositions into the soil as the 'water is absorbedtherein. Dust compositions, granular'compositions or liquid formulationsapplied on the surface of the soil can be distributed below the surfaceof the soil by conventional means such as discing, dragging or mixingoperations.

The phytotoxic compositions of this invention can also contain otheraddicaments, for example, fertilizers, pesticides andthe like, used asadjuvant or in combination with any of the above-describedadjuvants..Phytotoxicants useful in combination with the above-describedcompounds include for example 2,4-dichlorophenoxyacetic acids, 2,4,5trichlorophenoxyacetic acid, 2-methyl-4- chlorophenoxyacetic acid andthesalts, esters and amides thereof; triazine derivatives, such as2,4-bis(3-methoxyroacetyl)hexamethylene imine, and-N,N-diethyl-a-bromoacetamide, and the like; benzoic acids such as3-amino- 2,5-dichlorobenzoic and; thiocarbamates, such as S-propyldipropylthiocarbamate; S-ethyl-dipropylthiocarbamate, S-ethyl-cyclohexylethylthiocarbamate, S-ethylhexahydrolg-azepine-l-carbothioate and the like. Fertilizers useful incombination'with the active ingredients include, for example, ammoniumnitrate, urea and superphosphate. Other useful additaments includematerials in which plant organisms take root and grow such as compost,manure, hum asa andt e k The compositions of the present invention weretested as foliage'fungicides. This test indicated protectant actionagainst fungi attacking plant foliage. Pinto-bean plants were sprayedwith three concentrations of dissolved or suspended chemical in water,1000, 500 and 100 parts per million (p.p.m.). The active compound wasdissolved in an appropriate solvent and further dispersed in water, andfor this purpose a surface active agent or wetting agent was employed tofacilitate formulation of the dispersions. After the sprayed plants weredried, they were inoculated with powdery mildew spores (Erysiphepolygoni). Results were read when disease symptoms were distinct onuntreated bean plants. Compound numbers 84 and 86 exhibited 75-99%control at 100 p.p.m. and compound number exhibited control at 100p.p.m. of the powdery mildew infection with no phytotoxicity.

Insecticidal evaluation tests The following insect species weresubjected to evaluation tests for insecticidal activity:

(1) Housefiy (HF)Musca domestica (Linn.)

(2) German roach (GR)BlatlelZa germanica (Linn.)-

(3) Salt-marsh caterpillar (SMC)'Estigmene acrea (Drury) (4) Milkweedbug (MWB)-Onc0peltus fasciatus (Dallas) (5) Lygus bug (LB)Lygus hesperus(Kight) Aliquots of the toxicants, dissolved in an appropriate solvent,were diluted in water containing 0.002% of wetting agent, Sponto 221(apolyoxyether of alkylated phenols blended with organic sulfonates). Testconcentrations ranged from 0.1% downward to that at which 50% mortalitywas obtained. In the tests for these species, 10 one-month old nymphs ofthe German cockroach and Lygus bug and two-week old nymphs of milkweedbug were placed in separate circular cardboard cages sealed on one endwith cellophane and covered by a cloth netting on the other. Testconcentrations for the Lygus bug ranged from 0.05% downward to that atwhich 50% mortality was obtained. Each of the aqueous suspensions of thecandidate compounds were sprayed onto the insects through the clothnetting by means of a hand spray gun. Percent mortality in each caserecorded after 72 hours and the ID-SO values expressed as precent oftoxicant in the aqueous spray was recorded.

For testing the salt marsh caterpillar, test solutions were prepared inan identical manner and at concentrations the same as for the Germancockroach and the milkweed bug above. Sections of bitter dock Rumexobtusifolus) leaves, 11.5 inches in length were immersed in the testsolutions for 10 to 15 seconds and placed on a wire screen to dry. Thedried leaf was placed on a moistened piece of filter paper in a Petridish and infested with 5-3rd instar larvae. Mortality of the larvae wasrecored after 72 hours and the LD-SO values are expressed as percentactive ingredient in the aqueous suspension.

The following procedure was used to test houseflies. A stock solutioncontaining 100 g./ml. of the toxicant in an appropriate solvent wasprepared. Aliquots of this solution were combined with 1 milliliter ofan acetonepeanut oil solution in a glass Petri dish and allowed to dry.The aliquots were there to achieve desired toxicant concentrationranging from 100 g. per Petri dish to that at which 50% mortality wasattained. The Petri dishes were placed in a circular cardboard cage,closed on the bottom with cellophane and covered on top with cloth 15netting. Twenty-five female houseflies were introduced into the cage andthe percent mortality was recorded after 48 hours. The LD-50 values areexpressed in terms of g. per 25 female flies. The result of theseinsecticidal evaluation tests are given in Table IV.

TABLE IV (LD-50 values) Percent Compound number HF G It LB SMC 8 g./25 90. 1 0. 05 0.01 8 0. 1 0. 05 0. 1 5 0. 05 0. 03 0. 005 5 0. 08 0. 01 0.01 30 0. 08 0. 05 0. 05 30 0. 1 0. 05 0. 05 30 0. 1 0.05 0.08 5 0. 08 O.03 0. O5 5 0. 1 0. 008 0. 03 30 0. 1 0. 01 0. 1 30 0. 1 0. 03 0. 1 30 0.1 0. 008 0. 1 30 01 0.05 01 30 0. 1 0. 05 0. 1 50 0.1 0.05 01 30 0. 1 0.03 0. 1 50 0. 1 0. 01 0. 1 80 0. 1 0. 05 0. 1 50 01 0.05 0.1 10 0. 1 0.05 0. 1 30 01 0.05 0.1 10 0. 1 0. 05 0. 1 5 0. 1 0. 05 0. 1 10 01 0.0501 20 0. 1 0. 1 3 0. 1 005 0. 1 3 0. 1 0. 003 0. 1 8 0. 1 0. 0. 05 8 0.1 0. 03 0. 1 8 0. 1 0. 05 0. 08 50 0. 1 0. 05 0. 05 8 0. 1 0. 05 0. 03 80. 1 0. 005 0. 05 80 0. 1 0.05 0. 1 5 0. 1 0. 008 0. 1 8 0. 1 0.05 0.150 01 0.05 01 0. 1 0. 05 0. 1 100 O.1 0.05 01 2. 5 0. 01 0. 005 0. 01 0.8 0. 005 0.001 0.01 1. 5 0. 01 0 001 0. 03 10 0. 1 0. 1 30 0. 1 0. 1 300. 1 0. 1 30 0. 1 0. 1 30 0. 1 0. 1 4 0. 05 0. 05 8 0. 05 0. 08 8 0. 10. 03 0. 1 0. 1 0. 03 0. 1 40 0. 1 0. 05 0. 1 50 0. 1 0. 05 0. 1 30 0. 10. 05 0. 1 7 0. 1 0. 03 0. 05 8 0. 1 0. 03 0. 05 5 0. 1 0. 005 0. 1 8 0.1 0.01 0. 05 7 0. 1 0. 05 0. 1 8 0. 1 0.05 0. 1 2. 5 0. 05 0. 005 0. 010 0. 03 0. 00s 05 7 03 0. 01 005 7 03 0. 01 0- 008 3 0. 03 0, 005 0. 0037 0. 03 0. 01 0. 005 a 0a 00s 0. 1 6 0. 03 0. 01 0. 1 7 0. 1 0. 03 0. 037 0. 1 0. 05 0. 1 4 0. 1 0.005 0- 00s 8 0. 1 0. 01 03 5 0. 1 0.01 0. 1 505 005 01 5 0. 1 008 0. 1 5 03 003 01 5 0. 1 0. 05 0. 1 6 0. 1 0. 005 0.03 5 0. 1 0. 03 0. 01 6 03 0. 003 0. 05 4 03 0. 01 0. 03 5 03 0. 03 0.03 4 08 0. 008 0. 05 4 0. 1 0. 03 0. 1 3 0. 05 0. 008 01 6 0. 03 0. 010. 001 3 0. 03 0. 005 0. 03 3 0. 01 0. 005 0. 005 8 0. 1 0. 01 0. 1 0 0.1 0. 03 0. 1 5 0. 1 0. 01 0. 1 4 0. 1 0. 005 0.05 2 0. 03 0. 003 0. 03 70. 1 0. 05 0. 1 8 0. 1 0. 03 0. 05

In testing against milkweed bug representative LD-SO results obtainedwere for compound numbers47, 55 and 560.0l%; for compound numbers 49, 67and 143 0.03%; compound number 64-0.05%; compound number 680.08% andcompound number 540.008%.

Compound number 55 is extremely useful in the control of European cornborer (Pyrausta nubilalis (Hiibner)).

The same test procedure as mentioned above for salt marsh caterpillarwas used for cotton bollworm (Heliothis zea (Boddie) except that leavesof Romaine lettuce were utilized as the host plant rather than bitterdock. The following compounds were found to be active against cottonbollworm: the LD-SO values obtained were (5), (54) and (143) 0.005%;(10) 0.01%; (13) 0.03%; (137) 0.001%; (55), (138), (141), and (142)0.003%; and (56) 0.008%.

The compounds were also found to be active against two-spotted mite(Tetranychus urticae (Koch)). Lima bean plants (Phaseolus sp.) wereutilized as the host plant and infested with 50 to mites of variousages. Twenty four hours after infestation, they were sprayed to thepoint of run 011 with aqueous suspension of the toxicant. Testconcentrations range from 0.05% to that at which 50% mortality wasobtained. The following compounds exhibited LD-SO values of 0.005 (9)and (56); 0.001% (55) and 0.008% (46).

The compounds were also found to be active against black bean aphid(Aphis fabae (Scop.)). The same test procedure as given for thetwo-spotted mite above was used for black bean aphid except thatnasturtium (Trapaeolum sp.) plants aproximately 2 to 3 inches tall wereused as the host plant. The following compounds exhibited LD-SO valuesof 0.005% (40); 0.005% (55); 0.003% (37);0.003% (38);0.003% (65);0.008%(56); and 0.008% (64).

Animal systemic evaluation tests Candidate test compounds, usuallyformulated in Tween-20 (polyoxyethylene (20) Sorbitan monolaurate), areadministered orally by stomach tube at an initial dosage of 400 mg./kg.to fasted male Swiss albino mice. Two hours after treatment, the miceare killed by cervical dislocation and both thighs are dissected fromeach test animal and placed in labeled glass vials. Each vial isinoculated with 10 newly hatched black blow fly larvae (Phormia regina(Meigen) and stored in an incubator at F. and 4050% relative humidity.Tissues from mice that die during the two hour holding period afteradministration of the compounds are processed in the same manner. Afterthe larvae had fed on the tissues for 48 hours, the vials are examinedand the percentage of larvae mortality in each is noted. If 80% or moreof the larvae are killed at the initial dosage, successively lowerdosages are then tested until the lowest dosage that killed at least 80%of the larvae is determined.

In this animal systemic insecticide evaluation test, compounds aretested further on guinea pigs, using the oral route of administration.The compounds are formulated as solutions or suspensions in Tween 20and'administered at an initial dosage of mg./kg. Twenty-four hours priorto treatment, the guinea pigs are Wounded and the wounds infested withlarvae of the black blow fly (Phormia regina (Meigen)). At four andtwenty-four hours after treatment, stable flies (Stomoxys calcitrans(L.)) are fed on the guinea pigs. Engorged flies are held for 24 hoursto see if they are killed by the blood they ingest. At 24 hours aftertreatment, the wounds are examined to see if the fly larvae are killedby the insecticide. If the larvae are alive, they are removed from thewounds. If any of the arthropods are killed at the initial dosage, thecandidate insecticides are administered at lower dosages until there wasno significant insecticidal activity. The following table gives theresultsof the mouse assay and guinea pig assay tests described above.

Lowest dosage (mg/kg.)

Mouse assay 1 Guinea pig assay 90% plus activity Blow fly against larvaestable flies -I e) Lethal to mice 80% plus active (me/ s) Lethal to' G.pig (mg. /kg.

Compound Number The test results indicate that these compounds arebiologically active and are useful as animal systemic insecticides. Thecompounds can be used as effective parasaticides by applying them in avariety of ways and at various concentrations, depending upon the natureand habitat of the parasite to be controlled.

The candidate compounds were employed in an in vitro tick assay. In thistest unfed lone star tick nymphs (Amblyomma americanum (L.)) wereconfined for 24 hours in cotton cloth that had been treated in acetonesolutions of the test compounds. The percentage of nymphal mortality wasthen observed; If 80% or more of the nymphs were killed at the initialscreening level of 1.0% for a given compound, the compound was testedfurther at lower levels. The compounds 5, 11, 17, 20, 23, 26, 3 1, 33, 36, 38, 61, 64 and 65 exhibited 80% or better control of the tick nymphsat Compound number 29 exhibited 80% or better control of the tick nymphsat 0.1% and compound number 32 exhibited 80% or better control at 1.0%concentrations. Compound number 28 at a concentration of 0.05% wasbetter than 80% lethal to tick nymphs Internal animal parasite'systemictests The following procedures describe the chemoprophylactic andchemotherapeutic eflicacy tests utilized to demonstrate the animalparasitology activity of the phosphoruscontaining oxime .carbamatecompositions of the present invention Test 1.-Unparasitized weanlingmice were offered medicated food for 1-2 .days prior to inducinginfections, and

termine the comparative eflicacy of the medications All mice weresacrificed after 21 days (the medication period) and the residualparasites found in the intestine were identified and counted Thesecounts in the medicated groups were compared to the unmedicated(controls) and a percent eificacy was assigned, (M/ICXl00)100=percentefiicacy Test 2.-Weanling mice were housed together with older pinworm(So) and (At) infected mice in a box with damp litter for to 21 days toallow a heavy pin worm infection containing all stages of oxyurid (Soand At) to naturally build up. At the end of this holding period, thepost-weanling littermates were weighed individually and dosed with thesubject compounds (suspended in Tween on a body weight basis. One to 3days later, these mice were sacrificed and the residual wormsidentified, counted and compared to the unmedicated controls. Examplesof efficacy observed for six compounds of the present invention aregiven in the following table.

TABLE VI [Internal animal systemic activity] (I) Dosage; P m

p.p.m. ercent e eac Compound Test or (2) y number procedure mgJkg. So At(1 500 100 100 (1) 2,000 80 100 (2) 50 85 85 (2) 100 65 85 (l) 500 100100 (l) 1, 000 100 100 (l) 1, 000 98 97 (1) 2,000 90 55 (2) 50 0 (2) 10030 (2) 200 100 (1) 250 100 100 (2) 50 85 (2) 100 100 100 (1) 1,000 100100 (2) 50 65 100 (2) 100 100 (2) 50 92 97 (2) 100 00 98 (1) 500 100 100(2) 50 95 95 000 100 100 (2) 50 70 (1) 1, 000 98 100 (2) 5O 98 65 (l)250 100 100 (2) 50 95 85 (1) 250 65 (2) 50 15 (1) 500 100 (2) 50 55 92(2) 50 90 95 (2) 50 00 100 (2) 50 98 80 (2 50 100 100 (2) 50 100 85 (1)250 100 100 (l) 500 100 100 (l) 500 100 100 1 250 95 31 (1) 500 100 100(l) 500 100 75 (1) 500 100 (1) 250 100 100 (2) 100 100 100 (1) 500 100(1) 500 100 (1) 500 100 100 (1) 500 100 (l) 500 (1) 15 25 100 0 (2) 12.5 100 100 (2) 12. 5 100 100 The compounds of the present invention areuseful as for a total of 21 days infections were administered per os 70effective insecticides, herbicides, and external and internal using100-300-embryonated ova/mouse of Syphacia abvelata (So) and 100-300embryonated ova/mouse of Aspiculuris tetraptera' (At) 1 i A suitablenumber fo'f unrn'edicated littermate mice also received the aboveinfection and served as control to deanimal parasiticides and areapplicable in a variety of ways at various concentrations. In practice,the compounds are formulated with an inert adjuvant utilizing methodswell known to those skilled in the art, thereby 5 making them suitablefor application and administration as 19 dusts, sprays, drenches and thelike in the form and manner required. The mixtures can be dispersed inwater with the aid of a wetting agent or they can be employed in organicliquid compositions, oil-in-water, water-in-oil emulsions, with orwithout the addition of wetting, dispersing or emulsifying agents.Administration of said parasiticidal compositions to animal for systemiccontrol of parasites can be in animal feedstulfs which contain feedcomponents of such as grain, grasses and the like, and certainbeneficial additives such as vitamins, proteins, fats, minerals andcarbohydrates. They can be given also in drinking water or skimmed milk,or in the form of tablets or capsules. Further methods of applicationinclude sprays, dyes, dips, dermal pourpon, subcutaneous administration,intramuscular injection and the like. The exact dose to be administeredto the animal is dependent upon the parasite to be controlled by theparticular compound employed, as described herein, as well as uponwhether the administration is to be a single dose or a multiple doseover a period of days. In general, it has been found that the systemicparasiticides of this invention can be administered orally orparenterally to warm blooded animals in amounts ranging from about 0.01to about 600 milligrams per kilogram of body weight.

What is claimed: 1. A compound having the formula in which X and Y areindependently selected from the group consisting of oxygen and sulfur;

R is selected from the group lower alkyl or lower alkoxy, having from 1to 6 carbon atoms, inclusive;

R is selected from the group consisting of lower alkyl, lower alkoxyhaving from 1 to 6 carbon atoms, inclusive, amino, loweralkyl-substituted amino and phenyl;

Q is selected from the group consisting of hydrogen, divalenttetramethylenediene-l,3, lower alkoxy or lower alkyl having from 1 to 4carbon atoms, inclusive, nitro, halogen and combinations thereof; andlower dialkyl substituted thionophosphoryloxy;

R is selected from the group consisting of hydrogen, lower alkyl havingfrom 1 to 4 carbon atoms and phenyl;

R is a carbamate in which R and R are independently selected from thegroup consisting of hydrogen; alkyl having from 1 to 10 carbon atoms,inclusive; substituted alkyl having 1 to 6 carbon atoms, inclusive, saidsubstituent is selected from the group consisting of hydroxyl, halogen,amino, dilower alkyl amino and lower alkoxy; lower alkenyl having from 2to 4 carbon atoms, inclusive; carboalkoxy alkyl having a total of from 3to 8 carbon atoms, inclusive; cycloalkyl having from 3 to 6 carbonatoms, inclusive; phenyl; naphthyl; substituted phenyl wherein saidsubstituents are selected from the group consisting of halogen, loweralkyl, lower alkoxy, lower thioalkyl, lower dialkylamino in which saidlower alkyl and lower alkoxy moieties having from 1 to 4 carbon atoms,inclusive, nitro, cyano, trifluoromethyl and combinations thereof.

2. A compound according to claim 1 in which R is C H 0, R is C H O, X isS and Q is H, and the C(R )-=NOR group is in the nuclear 4-position inwhich Rg Hfl q giSCQQiNHCHa:

3. A compound according to claim 1 in which R is C H O, R is C H O, X isS and Q is H, and the group is in the nuclear 4-position in which R is Hand R is C(O)NHCH CH=CH 4. A compound according to claim 1 in which R isC H O, R is C H O, X is S and Q is H, and the group is in the nuclear2-position in which R; is H and R is C(O)NHCH CH=CH 5. A compoundaccording to claim 1 in which R is C2H50, R1 is C2H50, X is S and Q isH, and the group is in the nuclear 4-position in which R;, is H and R isC(O)NH(CH CH 6. A compound according to claim 1 in which R is (BI-I 0, Ris CH O, X is S, Q is H, and the C(R )=NOR group is in the nuclear4-position in which R is H and R is C(O)NHCH(CH 7. A compound accordingto claim 1 in which R is CH O, R is CH O, X is S, Q is H, and the C(R)=NOR group is in the nuclear 4-position in which R; is CH;, and R isC(O)NHCH 8. A compound according to claim 1 in which R is C1H50, R1 is CH O, X iS S and Q iS H, and the 9. A compound according to claim 1 inwhich R is C H O, R is C H O, X is S and Q is H, and the group is in thenuclear 4-position in which R is CH and R3 is 10. A compound accordingto claim 1 in which R is C H O, R is C H X is S, Q is H and the C(R =NORgroup is in the nuclear 4-position in which R is H and R is C(O)NHCH 11.A compound according to claim 1 in which R is C H O, R is C H X is S, Qis H and the C(R =NOR group is in the nuclear 4-position in which R is Hand R is C(O)NH-3-chloro-phenyl.

12. A compound according to claim 1 in which R is C H O, R is C H X isS, Q is H, and the C(R =NOR group is in the nuclear 4-position in whichR is H and R is C(O)NHCH CH==CH 13. A compound according to claim 1 inwhich R is C H O, R is C H O, X is S and Q is H, and the group is in thenuclear 4-position in which R is H and R is C(O)N(CH 14. A compoundaccording to claim 1 in which R is C H O, R is C H O, X is S and Q is H,and the C(R =NOR group is in the nuclear 4-position in which R is H andR is C(O)NHCH 15. A compound according to claim 1 in which R is C H O, Ris C H O, X is S and Q is 2-Cl, and the C(R )=NOR group is in thenuclear 4-position in which R; is H and R is C(O)NH-i-C H 16. A compoundaccording to claim 1 in which R is C H O, R is C H O, X is S and Q is2-Cl, and the C(R =NOR group is in the nuclear 4-position in which R isH and R is C(O)NHC H 17. A compound according to claim 1 in which R C HR is i-C H O, X is S and Q is H and the C a) =NOR 21 group is in thenuclear 4,-position in which R is H and R is C(O)NHCH 18. A compoundaccording to claim 1 in which R is C H R is i-C H O, X is S and Q is H,and the group is in the nuclear 4-position in which R is H and R isC(O)NHCH CH=CH 19. A compound according to claim 1 in which R is C H Ris i-C H O, X is S and Q is H, and the C (R =NOR group is in the nuclear4-position in which R is H and R is C(O)NH-3-chloro-phenyl.

20. A compound according to claim 1 in which R is C2H50, R1 is C2H50, XiS S, and Q is 2-CH3O and the C(Rg) =NOR group is in the nuclear4-position in which R is H and R is C(O)NHCH 21. A compound according toclaim 1 in which R is C H O, R is C H O, X is S and Q is H, and the C(R)=NOR group is in the nuclear 4-position in which R is CH and R isC(O)NHC H -n.

22. A compound according to claim 1 in which R is C H O, R is C H O, Xis S, and Q is 3-CH and the C(R =NOR group is in the nuclear 4-positio-nin which R3 is CH3 and R3 is 23. A compound according to claim 1 inwhich R is C H O, R is C H O, X is S and Q is H, and the C(R =NOR groupis in the nuclear 4-position in which R is CH and R is C(O)NH 24. Acompound according to claim 1 in which R is C H O, R is C H O, X is Sand Q is H, and the C(R )=NOR group is in the nuclear 4-position inwhich R is CH, and R3 is 25. A compound according to claim 1 in which Ris C H O, R is C H O, X is S and Q is H, and the C(R =NOR group is inthe nuclear 4-position in which R is H and R is C(O)NH-3-chloro-4-methylphenyl.

26. A compound according to claim 1 in which R is C2H50, R is C H O, Xis S and Q is H and the C(R )-=NOR group is in the nuclear 4-position inwhich R is H and 27. A compound according to claim 1 in which R is C l-I0, R is C H O, X is S and Q is H and the 2)= 3 group is in the nuclear4-position in which R is H and R is C(O)NH-phenyl.

28. A compound according to claim 1 in which R is C H O, R is C H O, Xis S and Q is H and the C(R )=NOR group is in the nuclear 4-position inwhich R; is H and R is C(O)NH-4-chloro-3-methylphenyl.

29. A compound according to claim 1- in which R is C I-I O, R is C H Xis S and Q is H and the group is in the nuclear 4-position in which R isH and R is C(O)NH-cyclohexyl.

30. A compound according to claim 1 in which R is C H O, R is C H 0, Xis S and Q is H and the group is in the nuclear 4-position in which R isH and R is C(O)NHC I-I OH.

31. A compound according to claim 1 in which R is C H O, R is C H O, Xis S and Q is H and the group is in the nuclear 4-position in which R isH and R is C(O)NH(N,N-diethylaminoethyl).

32. A compound according to claim 1 in which R is C l-I 0, R is C H O, Xis S and Q is H and the group is in the nuclear 4-position in which R isH and R is C(O)NH-3-methylthiophenyl.

33. A compound according to claim 1 in which R is C H O, R is C H O, Xis S and Q is 2-Cl, and the C(R )=NOR group is in the nuclear 4-positionin which R is H and R is C(O)NH-3-chlorophenyl.

34. A compound according to claim 1 in which R is C H O, R is C H X is Sand Q is H, and the C (5R2) '=NOR3 group is in the nuclear 4-position inwhich R is H and R is C(O)NHCH C(O) OC H 35. A compound according toclaim 1 in which R is 01-1 0, R is (II-I 0, X is S and Q is H and theC(R )=NO'R group is in the nuclear 4-position in which R is H and R isC(O')N(CH3)2- 36. A compound according to claim 1 in which R is C H O, Ris C H O, X is S and Q is H and the group is in the nuclear 4-positionin which R is H and R is C(O)NH-3-trifluoromethylphenyl.

37. A compound according to claim 1 in which R is CH O, R is CH O, X isS, Q is 4-Br and the group is in the nuclear 2-position in which R is Hand R is C(O)NHCH 38. A compound according to claim 1 in which R is CHO, R is CH O, X is S, Q is 4-Br and the C (R =NOR group is in thenuclear 2-position in which R; is H and R is C(O)NHCH(CH 39. A compoundaccording to claim 1 in which R is C2H50, R1 is C2H5O, X iS S, Q iS4-B1' and the group is in the nuclear Z-position in which R is H and Ris C(O)NHCH3.

40. A compound according to claim 1 in which R is CQHEO, R is C H O, Xis S, Q is 4-Br and the C CR2 group is in the nuclear 2-position inwhich R is H and R is C(O)NHCH 41. A compound according to claim 1 inwhich R is C H O, R is C H O, X is S and Q is H and the group is in thenuclear 4-position in which R is CH and R is C(O)NHCH 42. A compoundaccording to claim 1 in which R is C H R is i-C H O, X is S, Q is H andthe group is in the nuclear 4-position in which R is H and R isC(O)NH-4-bromophenyl.

43. A compound according to claim 1 in which R is C H O, R is NH X is S,Q is H, and C(R )'=NOR group is in the nuclear 4-position in which R isH and R is C(O)NHCH 23 24 44. A co mpound according to claim 1' in whichR is LEWIS GO'ITS, Primary Examiner CZHSO R1 C2H5O X 15 S and Q 15 H andthe A. H. SUTTO, Assistant Examiner C(R )=N0R group is in the nuclear4-position in which R is H and R is C(O)NH-n-C H 5 7186, 87; 260-239 BC,247.1, 247.5 R, 247.7 A, 268 C, 293 R, 293.4 B, 294.7 A, 306.7, 307 F,309.2, 309.6, 310 References Cited R, 326.1 I, 326.8, 326.82, 455 P,930, 940, 949; 424200, UNITED STATES PATENTS 211 2,816,128 12/1957 Allen260-920 10

